Regioselectivity and stereoselectivity of dioxygenase catalysed cis-dihydroxylation of mono- and tri-cyclic azaarene substrates.
cis-Dihydrodiol metabolites were obtained from dioxygenase-catalysed asymmetric dihydroxylations of five monocyclic (azabiphenyl) and four tricyclic (azaphenanthrene) azaarene substrates. Enantiopurity values and absolute configuration assignments were determined using a combination of stereochemical correlation, X-ray crystallography and spectroscopy methods. The degree of regioselectivity found during cis-dihydroxylation of monocyclic azaarenes (2,3 bond >> 3,4 bond) and of tricyclic azaarenes (bay region > non-bay region bonds) was dependent on the type of dioxygenase used. The cis-dihydrodiol metabolite from an azaarene (3-phenylpyridine) was utilised in the chemoenzymatic synthesis of the corresponding trans-dihydrodiol.
Boyd
Derek R
DR
School of Chemistry and Chemical Engineering, The Queen's University of Belfast, Belfast, BT9 5AG, UK. dr.boyd@qub.ac.uk
Sharma
Narain D
ND
Coen
Gerard P
GP
Hempenstall
Francis
F
Ljubez
Vera
V
Malone
John F
JF
Allen
Christopher C R
CC
Hamilton
John T G
JT
D001372:Aza Compounds / Q000737:chemistry* / Q000378:metabolism*; D001554:Benzene / Q000737:chemistry / Q000378:metabolism; D055162:Biocatalysis; D049308:Dioxygenases / Q000737:chemistry / Q000235:genetics / Q000378:metabolism*; D006900:Hydroxylation; D016297:Mutagenesis, Site-Directed; D010616:Phenanthrenes / Q000737:chemistry / Q000378:metabolism; D013237:Stereoisomerism; D013379:Substrate Specificity
D001372:Aza Compounds; D010616:Phenanthrenes; C031181:phenanthrene; D049308:Dioxygenases; D001554:Benzene